An agarose-based TOCN-ECM bilayer lyophilized-hydrogel with hemostatic and regenerative properties for post-operative adhesion management.

This study used a unique approach by developing a bilayer system that can simultaneously accomplish non-adhesion, hemostatic, and tissue regenerative properties. In this system, agarose was used as a carrier material, with an agarose-TEMPO-oxidized cellulose nanofiber (TOCN), (AT) layer acting as a non-adhesion layer and an Agarose-Extracellular matrix, (AE) layer acting as a tissue regenerative layer. Thrombin was loaded on the AE layer as an initiator of the healing process, by hemostasis. AT 1:4 showed 79.3 % and AE 1:4 showed 84.66 % cell viability initially confirming the biocompatible nature of the layers. The AE layer showed cell attachment and proliferation on its surface whereas on the AT layer, cells are visible but no attachment was observed. Furthermore, in vivo analysis was conducted. The non-adhesive layer was grafted between the cecum and peritoneal wall which showed that (AT 1:4) displayed remarkable non-adhesion properties as compared to a commercial product and the non-treated group. Hemostasis and tissue regeneration ability were evaluated using rat liver models. The bleeding time of AE 1:4TH was recorded as 160 s and the blood loss was 5.6 g. The results showed that (AE 1:4) displayed effective regeneration ability in the liver model after two weeks.

Highly Flexible, Self-Bonding, Self-Healing, and Conductive Soft Pressure Sensors Based on Dicarboxylic Cellulose Nanofiber Hydrogels.

Conductive hydrogels have gained a great deal of interest in the flexible electronics industry because of their remarkable inherent properties. However, a significant challenge remains for balancing hydrogel's conductivity, self-healing, and strength properties. Herein, double network ionic hydrogels were fabricated by concurrently introducing borax into dicarboxylic cellulose nanofiber (DCNFs) and polyacrylamide (PAM) hydrogels. The incorporation of borax provided a superabsorbent feature to the PAM/DCNF hydrogels (without borax) with the equilibrium water absorption rate increased from 552 to 1800% after 42 h. The compressive strength of the prepared hydrogel was 935 kPa compared to 132 kPa for the PAM hydrogel, with high cycling stability (stable after 1000 compression cycles with 50% strain). The hydrogel pressure sensor had a very sensitive response (gauge factor = 1.36) in the strain range from 10 to 80%, which made it possible to detect mechanical motion accurately and reliably. The developed hydrogels with high-performance, environmentally friendly properties are promising for use in future artificial skin and human-machine interface applications.

Nano cellulose-laden alginate/chitosan sponge with enhanced biological and hemostatic behavior.

Present study describes about hybrid hemostat developed with alginate (Alg), chitosan (Chito) and TEMPO-oxidized nanofibrillar cellulose (TOCNF) via lyophilization. All samples were analyzed under scanning electron microscopy (SEM) to determine their microstructure, size, and distribution of pores. Cell viability and proliferation of the scaffolds tested using fibroblast type L929 cells, showed it to be an excellent medium for cell generation. Blood coagulation started in ∼7.5 min, and most of the fibrin network formation took place in the Alg-Chito-TOCNF sponge, making it a suitable hemostatic material.

Ice-Crystal-Templated "Accordion-Like" Cellulose Nanofiber/MXene Composite Aerogels for Sensitive Wearable Pressure Sensors.

Exfoliated MXene nanosheets are integrated with cellulose nanofibers (CNFs) to form composite aerogels with high electric conductivity. The combination of CNFs and MXene nanosheets forms a unique "accordion-like" hierarchical architecture with MXene-CNF pillared layers through ice-crystal templating. Benefiting from the special "layer-strut" structure, the MXene/CNF composite aerogels have low density (50 mg/cm3), excellent compressibility and recoverability, as well as superior fatigue resistance (up to 1000 cycles). When being used as a piezoresistive sensor, the composite aerogel exhibits high sensitivity upon different strains, stable sensing performance with various compressive frequencies, broad detection range, and quick responsiveness (0.48 s). Moreover, the piezoresistive sensors are shown to have an excellent real-time sensing ability for human motions such as swallowing, arm bending, walking, and running. The composite aerogels also have a low environmental impact with the natural biodegradability of CNFs. The designed composite aerogels can serve as a promising sensing material for developing next-generation sustainable and wearable electronic devices.

Decellularized liver extracellular matrix and thrombin loaded biodegradable TOCN/Chitosan nanocomposite for hemostasis and wound healing in rat liver hemorrhage model.

During deep noncompressible wound management, surgery, transplantation or post-surgical hemorrhage, rapid blood absorption and hemostasis are the key factors to be taken into consideration to reduce unexpected deaths from severe trauma. In this study, a novel hemostatic biodegradable nanocomposite was fabricated where decellularized liver extracellular matrix (L-ECM) was loaded with two natural polymers (oxidized cellulose and chitosan) in association with thrombin. Plant-derived oxidized cellulose nanofiber (TOCN) and Chitosan (CS) from deacylated chitin were self-assembled with each other by electrostatic interactions. ECM was prepared by the whole tissue decellularization process and incorporated into the composite as a source of collagen and other integrated growth factors to promote wound healing. Thrombin was also anchored with the polymers by freeze drying for enhanced hemostatic efficiency of the composite. This study is the first of its kind to report non-solubilized L-ECM and thrombin loaded TOCN and CS composite, CN/CS/EM-Th for faster hemostasis effect in a rat tail amputation (~71 s) and liver avulsion model (~41 s). Furthermore, excellent liver wound regeneration efficacy was observed in-vivo in comparison to the commercially available oxidized regenerated cellulose product SURGICEL gauge.

Effectiveness of cellulose and chitosan nanomaterial coatings with essential oil on postharvest strawberry quality.

Polysaccharide materials, including bagasse cellulose nanocrystals (BCNCs), chitosan nanofibers (ChNFs), and sodium alginate (SA), were blended with oregano essential oil (OEO) to make single- and multi-polysaccharide edible coating suspensions. The prepared suspensions were spray-coated on strawberry surface to form thin films with thickness varying from about 570 to 790 nm for single-polysaccharide coatings and 690-930 nm for multi-polysaccharide coatings. The coatings made with multi-polysaccharide were more effective in inhibiting fungal growth compared with single-polysaccharide coatings. Strawberry treated with SA/BCNC/ChNF/OEO formulation had only 10.8 % weight loss after nine days of storage. In contrast, uncoated and single-polysaccharide coated strawberries had >37.0 % and 28.6 % weight loss, respectively. In addition, the SA/BCNC/ChNF/OEO coating retained desired moisture, respiration rate, stiffness, firmness, and appearance properties of strawberry due to its gas barrier properties resulting from the entangled matrix structure. These results suggest that the multi-polysaccharide suspensions with OEO have a high potential for application as edible coatings for retarding senescence of strawberries.

Transparent and Multi-Foldable Nanocellulose Paper Microsupercapacitors.

Despite the ever-increasing demand for transparent power sources in wireless optoelectronics, most of them have still relied on synthetic chemicals, thus limiting their versatile applications. Here, a class of transparent nanocellulose paper microsupercapacitors (TNP-MSCs) as a beyond-synthetic-material strategy is demonstrated. Onto semi-interpenetrating polymer network-structured, thiol-modified transparent nanocellulose paper, a thin layer of silver nanowire and a conducting polymer (chosen as a pseudocapacitive electrode material) are consecutively introduced through microscale-patterned masks (which are fabricated by electrohydrodynamic jet printing) to produce a transparent conductive electrode (TNP-TCE) with planar interdigitated structure. This TNP-TCE, in combination with solid-state gel electrolytes, enables on-demand (in-series/in-parallel) cell configurations in a single body of TNP-MSC. Driven by this structural uniqueness and scalable microfabrication, the TNP-MSC exhibits improvements in optical transparency (T = 85%), areal capacitance (0.24 mF cm-2 ), controllable voltage (7.2 V per cell), and mechanical flexibility (origami airplane), which exceed those of previously reported transparent MSCs based on synthetic chemicals.

Liver tissue-derived ECM loaded nanocellulose-alginate-TCP composite beads for accelerated bone regeneration.

Guided bone regeneration with osteoinductive scaffolds is a competitive edge of tissue engineering due to faster and more consistent healing. In the present study, we developed such composite beads with nanocellulose reinforced alginate hydrogel that carriedß-tricalcium phosphate (ß-TCP) nano-powder and liver-derived extracellular matrix (ECM) from porcine. Interestingly, it was observed that the beads' group containing ECM-ß-TCP-alginate-nanocellulose (ETAC) was more cytocompatible than the others comprised ofß-TCP-alginate-nanocellulose (TAC) and alginate-nanocellulose (AC). Cell attachment on ETAC beads was dramatically increased with time. In parallel within vitroresults, ETAC beads produced uniform cortical and cancellous bone in the femur defect model of rabbits within 2 months. Although the group TAC also produced noticeable bone in the defect site, the healing quality was improved and regeneration was faster after adding ECM. This conclusion was not only confirmed by micro-anatomical analysis but also demonstrated with x-ray microtomography. In addition, the characteristic moldable and injectable properties made ETAC a promising scaffold for clinical applications.

Fabrication of thrombin loaded TEMPO-oxidized cellulose nanofiber-gelatin sponges and their hemostatic behavior in rat liver hemorrhage model.

Excessive blood loss due to trauma or major surgical intervention can be life threatening which necessitates rapid hemorrhage management for the prevention of such bleeding related sufferings. Broad interest in developing new hemostatic technologies have been paid for bleeding control but none of them found completely satisfactory especially in terms of rapid clotting, absorbability, porosity, cost effectiveness and safety. To address these issues, a combination of active and passive hemostatic materials from biological sources could be a wise choice. Therefore, plant-derived TEMPO-oxidized nanocellulose (TOCN)/biopolymer gelatin (G) sponge was successfully prepared in co-operation with intrinsic blood coagulation enzyme thrombin (Th) via freeze drying method and their application as rapid hemostatic dressing was investigated. Morphological and in vitro characteristics of the samples were evaluated where uniformity, porosity, swelling, degradation behavior had direct relationship with the percent gelatin incorporation. In vitro hemocompatibility and cyto-compatibility of these sponges were confirmed as well. Among the samples, TOCN 2.5G-Th sponge exhibited excellent hemostatic effect, rapid absorbability, minimum clotting time (1.37 ± 0.152 min) and reduction of blood loss was ensured through rat liver punch biopsy model. The results demonstrated that, Th enhanced blood coagulation, platelet and red blood cell aggregation following application of biopolymer TOCN 2.5G-Th sponge compared with samples devoid of Th. In short, the functional, cost effective and nontoxic sponge developed via facile preparation could potentially be used as an absorbable biomaterial to achieve immediate hemostasis. HighlightsPlant-derived TEMPO-oxidized nanocellulose (TOCN) and biopolymer gelatin (G) was successfully used to prepare a hemostatic sponge in combination with intrinsic blood coagulation enzyme thrombin (Th).The TG sponge combines the advantages of TOCN and gelatin, exhibiting biocompatibility, biodegradability and superior blood-absorption performance.The TOCN 2.5G-Th sponge improves plasma absorption, red blood cell adhesion, aggregation, platelet adhesion and activation leading to enhanced hemostasis effect and shorter hemostasis time in vitro and in vivo.

Wet-Spun Composite Filaments from Lignocellulose Nanofibrils/Alginate and Their Physico-Mechanical Properties.

Lignocellulose nanofibrils (LCNFs) with different lignin contents were prepared using choline chloride (ChCl)/lactic acid (LA), deep eutectic solvent (DES) pretreatment, and subsequent mechanical defibrillation. The LCNFs had a diameter of 15.3-18.2 nm, which was similar to the diameter of commercial pure cellulose nanofibrils (PCNFs). The LCNFs and PCNFs were wet-spun in CaCl2 solution for filament fabrication. The addition of sodium alginate (AL) significantly improved the wet-spinnability of the LCNFs. As the AL content increased, the average diameter of the composite filaments increased, and the orientation index decreased. The increase in AL content improved the wet-spinnability of CNFs but deteriorated the tensile properties. The increase in the spinning rate resulted in an increase in the orientation index, which improved the tensile strength and elastic modulus.

Multi-functional nanocellulose-chitosan dressing loaded with antibacterial lawsone for rapid hemostasis and cutaneous wound healing.

Cutaneous wounds accompanied by massive bleeding, bacterial infections might be lethal and cause fundamental therapeutic impediments in clinical fields. As part of the push for a solution, biomaterial having hemostatic-antibacterial features is highly desirable. Inspired by this concept, freeze dried sponges were developed followed by combining tempo-oxidized nanocellulose (TOCN), chitosan using EDC/NHS cross-linker with antibacterial lawsone loading for controlled delivery of this compound during wound healing. The pore diameter decreased upon increasing chitosan (2.5, 3.5, 4.5, 5.5% w/v) while TOCN ensured scaffold's mechanical stability. The in vitro degradation, lawsone release from fibroblast cell-compatible sponge was faster in acidic pH 5.5 than physiologic pH 7.4 indicating adaptability to physiological skin milieu of wounds. The rat tail amputation model, 14 days rat full-thickness cutaneous-wound model ensured hemostasis, dramatic wound closure after TLC4.5 (optimized scaffold) treatment suggesting its potential as functional wound healing substitute showing obvious avenue for hemostatis and skin tissue reconstruction arena.

Preparation and Properties of Wet-Spun Microcomposite Filaments from Various CNFs and Alginate.

We aimed to improve the mechanical properties of alginate fibers by reinforcing with various cellulose nanofibrils (CNFs). Pure cellulose nanofibril (PCNF), lignocellulose nanofibril (LCNF) obtained via deep eutectic solvent (DES) pretreatment, and TEMPO-oxidized lignocellulose nanofibril (TOLCNF) were employed. Sodium alginate (AL) was mixed with PCNF, LCNF, and TOLCNF with a CNF content of 5-30%. To fabricate microcomposite filaments, the suspensions were wet-spun in calcium chloride (CaCl2) solution through a microfluidic channel. Average diameters of the microcomposite filaments were in the range of 40.2-73.7 µm, which increased with increasing CNF content and spinning rate. The tensile strength and elastic modulus improved as the CNF content increased to 10%, but the addition of 30% CNF deteriorated the tensile properties. The tensile strength and elastic modulus were in the order of LCNF/AL > PCNF/AL > TOLCNF/AL > AL. An increase in the spinning rate improved the tensile properties.

Carbonized Cellulose Nanofibril with Individualized Fibrous Morphology: toward Multifunctional Applications in Polycaprolactone Conductive Composites.

Drying cellulose nanofibril (CNF) from aqueous suspensions often leads to aggregated fibril morphology, negatively affecting its performance in ensuing applications. In this work, we introduced a new solvent drying approach to acquire dry CNF from aqueous suspensions and subsequently pyrolyzed the CNF precursor to obtain carbonized CNF (CCNF) without loss of its fibrous morphology. The fibrous CCNF was dispersed homogeneously in polycaprolactone (PCL) thermoplastic resin, greatly enhancing PCL composite tensile performance. After being further mixed with carbon black (CB), the CCNF helped to minimize CB aggregation due to formation of interconnected three-dimensional (3D) structures. The CCNF/CB/PCL composite exhibited superior electrical conductivity ascribed to electrons transporting more efficiently among CB aggregates. The composite is also suitable for applications such as 3D printed electromagnetic interference (EMI) shielding and deformation sensing. Specifically, the 3D printed EMI shielding composite efficiently absorbed EM radiation in the frequency range of 4-26 GHz, and the 3D printed deformation sensor exhibited excellent sensitivity, durability, and flexibility in monitoring mechanical distortions. Herein, this study sheds light on the development of multifunctional conductive composites embedded with fibrous CCNF from sustainable resources.

Effects of Methylenediphenyl 4,4'-Diisocyanate and Maleic Anhydride as Coupling Agents on the Properties of Polylactic Acid/Polybutylene Succinate/Wood Flour Biocomposites by Reactive Extrusion.

Polylactic acid (PLA)/polybutylene succinate (PBS)/wood flour (WF) biocomposites were fabricated by in situ reactive extrusion with coupling agents. Methylenediphenyl 4,4'-diisocyanate (MDI) and maleic anhydride (MA) were used as coupling agents. To evaluate the effects of MDI and MA, various properties (i.e., interfacial adhesion, mechanical, thermal, and viscoelastic properties) were investigated. PLA/PBS/WF biocomposites without coupling agents revealed poor interfacial adhesion leading to deteriorated properties. However, the incorporation of MDI and/or MA into biocomposites showed high performances by increasing interfacial adhesion. For instance, the incorporation of MDI resulted in improved tensile, flexural, and impact strengths and an increase in tensile and flexural modulus was observed by the incorporation of MA. Specially, remarkably improved thermal stability was found in the PLA/PBS/WF biocomposites with 1 phr MDI and 1 phr MA. Also, the addition of MDI or MA into biocomposites increased the glass transition temperature and crystallinity, respectively. For viscoelastic property, the PLA/PBS/WF biocomposites with 1 phr MDI and 1 phr MA achieved significant enhancement in storage modulus compared to biocomposites without coupling agents. Therefore, the most balanced performances were evident in the PLA/PBS/WF biocomposites with the hybrid incorporation of small quantities of MDI and MA.

Preparation and Characteristics of Wet-Spun Filament Made of Cellulose Nanofibrils with Different Chemical Compositions.

In this study, wet-spun filaments were prepared using lignocellulose nanofibril (LCNF), with 6.0% and 13.0% of hemicellulose and lignin, respectively, holocellulose nanofibril (HCNF), with 37% hemicellulose, and nearly purified-cellulose nanofibril (NP-CNF) through wet-disk milling followed by high-pressure homogenization. The diameter was observed to increase in the order of NP-CNF ≤ HCNF < LCNF. The removal of lignin improved the defibrillation efficiency, thus increasing the specific surface area and filtration time. All samples showed the typical X-ray diffraction pattern of cellulose I. The orientation of CNFs in the wet-spun filaments was observed to increase at a low concentration of CNF suspensions and high spinning rate. The increase in the CNF orientation improved the tensile strength and elastic modulus of the wet-spun filaments. The tensile strength of the wet-spun filaments decreased in the order of HCNF > NP-CNF > LCNF.

Thermal stimuli-responsive hyaluronic acid loaded cellulose based physical hydrogel for post-surgical de novo peritoneal adhesion prevention.

Effective strategies for post-surgical adhesion prevention have increasingly focused on injectable adhesion barriers due to their minimal invasiveness and wider applicability. In this study, a thermo-reversible hydrogel was developed by combining high molecular weight hyaluronic acid (HA) at various concentrations (0.05, 0.25, and 0.45% w/v) with tempo-oxidized nanocellulose (TOCN), methyl cellulose (MC) and polyethylene glycol (PEG) for anti-adhesion application. The hydrogel preparation time was short and did not require any chemical modification. TOCN ensured the mechanical stability of the hydrogel. MC confirmed thermo-sensitive feature. Higher amounts of HA increased the rate of hydrogel degradation. The HA 0.25 hydrogel was free-flowing, injectable at ambient temperature, capable of faster (40 ± 2 s), and reversible sol-gel (4 °C-37 °C) transition. A rat side-wall cecum abrasion model was used to confirm the complete de novo adhesion prevention efficacy of optimized HA 0.25 hydrogel, where the scratched abdominal wall of animals treated with HA 0.25 hydrogel healed after 14 days. During in vivo experiment, PEG in the hydrogel played a crucial role in adhesion prevention by minimizing friction between the surgical site and nearby organs. In a nutshell, HA 0.25 hydrogel, fabricated without crosslinking agent, is a potential candidate for tissue adhesion prevention strategies.

Poly(acryloyl hydrazide)-grafted cellulose nanocrystal adsorbents with an excellent Cr(VI) adsorption capacity.

In this study, we prepared poly(acryloyl hydrazide) (PAH)-grafted cellulose nanocrystal (CNC-PAH) particles via the atom transfer radical polymerization method for application to Cr(VI) adsorption. The closely-packed PAH chains grafted on the cellulose nanocrystal (CNC) surface provide a high density of amine groups that can adsorb Cr(VI) through strong electrostatic, hydrogen bonding and chelating interactions. CNC-PAH exhibited the optimum Cr(VI) adsorption capacity at the solution pH = 3, where its electrostatic attraction with Cr(VI) was maximized. Cr(VI) was chemisorbed in CNC-PAH by following the Langmuir isotherm mechanism (homogeneous monolayer adsorption). The Cr(VI) adsorption kinetics of CNC-PAH was controlled predominantly by intra-particle diffusion resistance imparted by the PAH shell layer. Thermodynamic analysis revealed that Cr(VI) adsorption of CNC-PAH is a spontaneous and endothermic process. Importantly, CNC-PAH grafted with the higher Mw (∼50 kg mol-1) PAH exhibited a rapid Cr(VI) adsorption rate and remarkably high Cr(VI) adsorption capacity (∼457.6 mg g-1 at 298.15 K), exceeding those of previously reported adsorbents owing to its numerous Cr(VI)-adsorptive amine groups provided by the closely-packed grafted PAH polymers. Furthermore, CNC-PAH showed excellent reusability to maintain its high adsorption ability during repeated adsorption-desorption cycles owing to the covalently binding nature of the PAH polymers.

Silver-Incorporated Nanocellulose Fibers for Antibacterial Hydrogels.

A free-standing, antibacterial hydrogel was fabricated using silver-nanoparticle-immobilized cellulose nanofibers (CNFs) and alginate. Surface hydroxyl groups of CNFs were oxidized to carboxylate groups using (2,2,6,6-tetramethylpiperidin-1-yl)oxidanyl (TCNF), followed by the treatment with silver nitrate solution for surface adsorption of silver ions. In situ reduction of silver ions to produce silver nanoparticles was performed for the silver-adsorbed CNFs. Electron microscopy, X-ray diffraction, and spectroscopic analysis revealed that higher amounts of silver nanoparticles were immobilized on the surface of TCNF than on the surface of native CNF. Silver-nanoparticle-immobilized TCNF was embedded in alginate gels and silver ions from the matrix were slowly released for 7 days. Silver-nanoparticle-loaded alginate gels showed comparable antibacterial activity to silver-ions-loaded alginate gels, although the former showed a significantly lower cytotoxicity against animal cells. Thus, the antibacterial gels can potentially be applied to various skin surfaces to prevent bacterial infection while minimizing skin damage.